Tetraphenylketazines and isoindolinone pigments obtained therefrom

ABSTRACT

Isoindolinone pigments of the formula ##STR1## wherein X 1 , X 2 , X 3  and X 4  represent hydrogen or halogen atoms, or one or two of X 1  -X 4  represents alkoxy groups of 1 to 4 carbon atoms of phenoxy groups and the others represent hydrogen or halogen atoms, R and R&#34; represent hydrogen or halogen atoms or methyl or methoxy groups, R 1 , R 2 , R 4  and R 5  represent hydrogen, chlorine or bromine atoms or alkyl groups of 1 to 2 carbon atoms, R 3  and R 6  represent hydrogen or halogen atoms, alkyl or alkoxy groups of 1 to 2 carbon atoms or radicals of the formula ##STR2## Q represents a direct bond or a p-phenylene group, n is 1 or 2 and X represents a group of the formula ##STR3## wherein R 7  and R 8  represent hydrogen or chlorine atoms or methyl groups.

This is a divisional of application Ser. No. 007,549, filed on Jan. 30,1979, now U.S. Pat. No. 4,231,931.

The invention provides novel isoindolinone pigments of the formula##STR4## wherein X₁, X₂, X₃ and X₄ represent hydrogen or halogen atoms,or one or two of X₁ -X₄ represent alkoxy groups of 1 to 4 carbon atomsor phenoxy groups and the others represent hydrogen or halogen atoms, Rand R" represent hydrogen or halogen atoms or methyl or methoxy groups,R₁, R₂, R₄ and R₅ represent hydrogen, chlorine, or bromine atoms oralkyl groups of 1 to 2 carbon atoms, R₃ and R₆ represent hydrogen orhalogen atoms, alkyl or alkoxy groups of 1 to 2 carbon atoms or radicalsof the formula ##STR5## Q represents a direct bond or a p-phenylenegroup, n is 1 or 2 and X represents a group of the formula ##STR6##wherein R₇ and R₈ represent hydrogen or chlorine atoms or methyl groups.

Preferred pigments are those of the formula (I) containingiminoisoinodolinone radicals of the formula ##STR7## wherein Halrepresents a chlorine or bromine atom, Y and/or Z represent chlorine orbromine atoms or alkoxy groups of 1 to 4 carbon atoms, and, inparticular, those pigments of the formula (I) wherein X₁, X₂, X₃ and X₄represent chlorine atoms.

Particularly preferred pigments are those of the formula (I) wherein R₃and R₆ represent hydrogen, chlorine or bromine atoms, methyl or methoxygroups in the para-position to X, and especially those of the formula(I), wherein Q is a direct bond and n is 1.

The pigments of the present invention are obtained by condensing 2 or 4moles of an isoindolinone of the formula ##STR8## wherein X₁, X₂, X₃ andX₄ are as previously defined and A represents a group of the formula##STR9## wherein Y₁ represents an imino or thio group and Y₂ representsa halogen atom, an alkoxy group of 1 to 4 carbon atoms or a secondaryamino group, with 1 mole of an amine of the formula ##STR10## wherein R,R", R₁, R₂, R₄ and R₅ are as previously defined and R₃ ' and R₆ 'represent hydrogen or halogen atoms, alkyl or alkoxy groups of 1 to 2carbon atoms or amino groups in the para-position to X, and Q is adirect bond or represents a p-phenylene group.

The preferred starting materials are isoindolinones of the formula##STR11## wherein the symbols R' represents alkyl groups of 1 to 4carbon atoms, Y and Z are as previously defined, and especially thoseisoindolinones wherein X₁ -X₄ in formula (II) represent chlorine atoms.

Examples of such isoindolinones are:

3-imino-isoindolinone

3-imino-4-chloro-isoindolinone

3-imino-5-chloro-isoindolinone

3-imino-6-chloro-isoindolinone

3-imino-7-chloro-isoindolinone

3-imino-5,6-dichloro-isoindolinone

3-imino-4,5-dichloro-isoindolinone

3,3-dimethoxy-4,5-dichloro-isoindolinone

3,3-dimethoxy-4,7-dichloro-isoindolinone

3,3-dimethoxy-4,5,6,7-tetrachloro-isoindolinone

3,3,6-trimethoxy-4,5,7-trichloro-isoindolinone

3,3-dimethoxy-4,5,7-trichloro-6-ethoxy-isoindolinone

3,3-dimethoxy-4,5,7-trichloro-6-n-propoxy-isoindolinone

3,3-dimethoxy-4,5,7-trichloro-6-n-butoxy-isoindolinone3,3-dimethoxy-4,5,7-trichloro-6-phenoxy-isoindolinone3,3,4,6-tetramethoxy-5,7-dichloro-isoindolinone.

The compounds are known ones or compounds which can be obtained by knownmethods.

The invention also provides the novel amines of the formula ##STR12##wherein R, R", R₁, R₂, R₄, R₅, R₃ ', R₆ ', Q, X and n are as previouslydefined. They are obtained by condensation of 1 mole of hydrazine with 1mole of an amine of the formula ##STR13## and with 1 mole of an amine ofthe formula ##STR14##

Amines used for the manufacture of the pigments of the formula (I) arepreferably those of the formula (III), wherein R₃ ' and R₆ ' representhydrogen, chlorine or bromine atoms, methyl or methoxy groups in thepara-position to X, and especially those wherein Q is a direct bond andn is 1.

The nomemclature used in the following Examples is derived from thetetraphenylketazine of the formula ##STR15## with the indicatednumbering. 4,4'-diamino-tetraphenylketazine

4,4'-diamino-4",4"'-dichloro-tetraphenylketazine

4,4'-diamino-4",4"'-dimethyl-tetraphenylketazine

4,4'-diamino-4",4"'-dimethoxy-tetraphenylketazine

4,4'-diamino-3,3',4",4"'-tetramethyl-tetraphenylketazine

4,4'-diamino-3,3'-dimethyl-4",4"'-dimethoxy-tetraphenylketazine

4,4'-diamino-4",4"'-diphenoxy-tetraphenylketazine

4,4'-diamino-4",4"'-diphenyl-tetraphenylketazine

4,4'-diamino-3,3'-dimethyl-4",4"'-diphenyl-tetraphenylketazine

4,4'-diamino-3",3"',4",4"'-tetrametheyl-tetraphenylketazine

4,4'-diamino-2",2"',4",4"'-tetrachloro-tetraphenylketazine

4,4'-diamino-3,3',3",3"',4",4"'-hexamethyl-tetraphenylketazine

4,4'-diamino-3,3'-dimethyl-2",2"',4",4"'-tetrachloro-tetraphenylketazine

4,4'-diamino-3",3"',4",4"'-tetramethoxy-tetraphenylketazine

4,4',4",4"'-tetramino-tetraphenylketazine

3",3"',4,4'-tetramino-tetraphenylketazine

3",3"',4,4'-tetramino-4",4"'-dichloro-tetraphenylketazine

4,4'-diamino-4",4"'-di-(o-aminophenoxy)-tetraphenylketazine

4,4'-diamino-4",4"'-di-(p-aminophenoxy)-tetraphenylketazine

4,4'-diamino-4",4"'-di-(p-amino-o-chlorophenoxy)-tetraphenylketazine.

The above amines can be obtained by condensation of the correspondingaminobenzophenones with hydrazine.

Where 3-imino-, 3-thio- or3,3-bis-sec-amino-4,5,6,7-tetrachloroisoindolin-1-ones or alkali saltsof 3,3-dialkoxy-4,5,6,7-tetrachloroisoindolin-1-ones are used asstarting materials, then it is advantageous to use water-miscibleorganic solvents, e.g. lower aliphatic alcohols, such as lower alkanols,for example methanol, isopropanol or butanol, lower cyclic ethers, suchas dioxan, ethylene glycol monomethyl ether, lower aliphatic ketones,such as acetone. In doing so, the condensation is able to take placeeven at relatively low temperatures. It is advantageous to perform thereaction in the presence of an agent binding alkali and organic bases,for example a lower fatty acid which can be used simultaneously assolvent, especially acetic acid.

If the starting material is a3,3-dihalogeno-4,5,6,7-tetrachloroisoindolin-1-one, it is preferred touse an organic solvent that does not contain hydroxyl groups, forexample an aromatic hydrocarbon, such as benzene, toluene, xylene,tetrahydronaphthalene or diphenyl; a cycloaliphatic hydrocarbon, forexample cyclohexane; a halogenated aliphatic hydrocarbon, for examplecarbon tetrachloride or tetrachloroethylene, or a halogenated aromatichydrocarbon, for example chlorobenzene or di- and trichlorobenzene; alsoa nitrated hydrocarbon, for example nitrobenzene; an aliphatic ether,for example dibutyl ether; an aromatic ether, for example diphenylether, or a cyclic ether, for example dioxan; also a ketone, for exampleacetone; or an ester, for example an ester of a lower fatty acid with alower alkanol, for example ethyl acetate, in the presence of an acidacceptor.

Directly after their formation the pigments of the present inventionprecipitate from the reaction medium. For certain purposes they can beused direct as crude pigments; but their properties, especially withrespect to purity, form, and hiding power, can also be improved by knownmethods, for example by extraction with organic solvents or by grindingwith grinding assistants which can afterwards be removed, for examplesalts, or by precipitation with an alkali.

The new colourants constitute valuable pigments which, in finely dividedform, can be used for pigmenting organic material of high molecularweight, for example cellulose ethers and esters, such as ethylcellulose, acetyl cellulose, nitrocellulose, polyamides andpolyurethanes or polyesters, natural resins or synthetic resins, such aspolymerisation or condensation resins, for example aminoplasts, inparticular urea/formaldehyde and melamine/formaldehyde resins, alkydresins, phenolic plastics, polycarbonates, polyolefins, such aspolystyrene, polyvinyl chloride, polyethylene, polypropylene,polyacrylonitrile, polyacrylates, thermoplastic or curable acrylicresins, rubber, casein, silicon and silicone resins, singly or inmixtures.

It is immaterial whether the cited materials of high molecular weightare in the form of plastics, melts or of spinning solutions, lacquers,paints or printing inks. Depending on the use to which they are put, itis advantageous to use the new pigments as toners or in the form ofpreparations.

The colourations obtained are characterised by high colour strength,great purity of shade, and good fastness to alkali, overstripe bleeding,light, migration and atmospheric influences.

The invention is illustrated by the following Examples in which thepercentages are by weight.

EXAMPLE 1

17.25 g of 3,4,5,6-tetrachlorocyanobenzoic acid methyl ester are stirredwith 57.5 ml of a 1 N sodium methylate solution in methanol until aclear solution is obtained. The sodium salt of3,3-dimethoxy-4,5,6,7-tetrachloroisoindolin-1-one forms. With goodstirring, 11.5 g of 4,4'-diamino-4",4"'-dichloro-tetraphenylketazine(ground and sieved) and 100 ml of o-dichlorobenzene are added. As a bathtemperature of 110° C., the internal temperature is raised in the courseof 2 hours to 90° C. while distilling off methano, whereupon the sodiumsalt of the pigment precipitates without a clear solution having formed.The batch is diluted with a further 100 ml of o-dichlorobenzene and,when the internal temperature has reached 100° C. (bath temperature 130°C.), acidified with 20 ml of glacial acetic acid. The temperature israised to 140°-150° C. and kept thereat for 2 hours with good stirring.The insoluble pigment is filtered off at 120° C., washed with methanol,acetone and water, and dried, to yield 24 g of a productive orangepigment, which in the form in which it is obtained, or after it has beenground by one of the conventional methods, can be used for colouringplastics and for obtaining printing pastes and lacquers. The orangecolourations obtained therewith are characterised by outstandingfastness properties.

    ______________________________________                                        Analysis                                                                      ______________________________________                                        calculated:   C 50.8    H 1.8   N 8.4                                         found:        C 51.0    H 2.1   N 8.8                                         ______________________________________                                    

EXAMPLE 2

An orange pigment with similar properties obtained by using3,4,5,6-tetrabromo-o-cyanobenzoic acid methyl ester instead of3,4,5,6-tetrachloro-o-cyanobenzoic acid methyl ester.

EXAMPLE 3

By using equimolar amounts of 3,4,6-trichloro-5-methoxy-o-cyanobenzoicacid methyl ester instead of 3,4,5,6-tetrachlorocyanobenzoic acid methylester, an orange pigment is obtained which, when incorporated intoplastics, printing pastes and lacquers, has similarly good properties.

EXAMPLES 4 TO 40

Table I lists further pigments which are obtained by condensing anisoindolinone of the formula ##STR16## wherein Y₁ and Z₁ have theindicated meanings, with a diamine of the formula ##STR17## wherein R,R₁, R₂, R₃, R₄ and Q have the indicated meanings.

                                      TABLE I                                     __________________________________________________________________________    No Y.sub.1                                                                           Z.sub.1                                                                           R  R.sub.1  R.sub.2                                                                           R.sub.3                                                                           R.sub.4                                                                           Shade                                      __________________________________________________________________________    1 Q = direct bond                                                             5  Cl  Cl  H  H        H   H   H   scarlet                                    6  Cl  Cl  CH.sub.3                                                                         H        H   H   H   scarlet                                    7  Cl  Cl  H  CH.sub.3 H   H   H   scarlet                                    8  Cl  OCH.sub.3                                                                         H  CH.sub.3 H   H   H   orange                                     9  Cl  Cl  CH.sub.3                                                                         CH.sub.3 H   H   H   red                                        10 Cl  Cl  H  OCH.sub.3                                                                              H   H   H   red                                        11 Cl  Cl  CH.sub.3                                                                         OCH.sub.3                                                                              H   H   H   red                                        12 OCH.sub.3                                                                         OCH.sub.3                                                                         H  Cl       H   H   H   yellow                                     13 Cl  Cl  CH.sub.3                                                                         Cl       H   H   H   orange                                     14 Cl  Cl  H  Br       H   H   H   orange                                     15 Cl  Cl  CH.sub.3                                                                         Br       H   H   H   orange                                     16 Cl  Cl  H  phenyl   H   H   H   scarlet                                    17 Cl  Cl  CH.sub.3                                                                         phenyl   H   H   H   red                                        18 Cl  Cl  H  phenoxy  H   H   H   yellow                                     19 Cl  Cl  H  CH.sub.3 CH.sub.3                                                                          H   H   scarlet                                    20 Cl  OCH.sub.3                                                                         H  CH.sub.3 CH.sub.3                                                                          H   H   orange                                     21 Cl  Cl  CH.sub.3                                                                         CH.sub.3 CH.sub.3                                                                          H   H   red                                        22 Cl  Cl  H  CH.sub.3 H   CH.sub.3                                                                          H   yellow                                     23 Cl  Cl  H  OCH.sub.3                                                                              OCH.sub.3                                                                         H   H   yellow                                     24 Cl  Cl  H  OCH.sub.3                                                                              H   OCH.sub.3                                                                         H   yellow                                     25 Cl  Cl  H  Cl       Cl  H   H   orange                                     26 Cl  OCH.sub.3                                                                         H  Cl       Cl  H   H   yellow                                     27 Cl  Cl  CH.sub.3                                                                         Cl       Cl  H   H   orange                                     28 Cl  OCH.sub.3                                                                         CH.sub.3                                                                         Cl       Cl  H   H   yellow                                     29 Cl  Cl  H  Cl       H   Cl  H   yellow                                     30 Cl  Cl  H  OC.sub.2 H.sub.5                                                                       H   H   H   orange                                     31 Cl  Cl  H  F        H   H   H   yellowish orange                           32 Cl  Cl  H  C.sub.2 H.sub.5                                                                        H   H   H   orange                                     33 Cl  Cl  H  H        H   OCH.sub.3                                                                         OCH.sub.3                                                                         yellow                                     34 Cl  Cl  CH.sub.3                                                                         F        H   H   H   orange                                     35 Cl  Cl  H  Cl       H   CH.sub.3                                                                          CH.sub.3                                                                          yellow                                     36 Cl  Cl  H  Cl       H   OCH.sub.3                                                                         OCH.sub.3                                                                         yellow                                     37 Cl  Cl  H  H        H   CH.sub.3                                                                          CH.sub.3                                                                          yellow                                     38 Cl  Cl  CH.sub.3                                                                         OC.sub.2 H.sub.5                                                                       H   H   H   red                                        39 Cl  Cl  CH.sub.3                                                                         C.sub.2 H.sub.5                                                                        H   H   H   scarlet                                    40 Cl  Cl  CH.sub.3                                                                          ##STR18##                                                                             H   H   H   orange                                      ##STR19##                                                                    41 Cl  Cl  H  H        H   H   H   orange                                     42 Cl  Cl  H  CH.sub.3 H   H   H   yellow                                     43 Cl  Cl  H  OCH.sub.3                                                                              H   H   H   yellow                                     44 Cl  Cl  H  Cl       H   H   H   yellow                                     __________________________________________________________________________

EXAMPLE 45

17.25 g of 3,4,5,6-tetrachloro-o-cyanobenzoic acid methyl ester arestirred with 57.5 ml of 1 N sodium methylate solution in methanol untila clear solution is obtained, whereupon the sodium salt of3,3-dimethoxy-4,5,6,7-tetrachloroisoindolinone forms. Then 5.25 g of4,4',4",4"'-tetraamino-tetraphenylketazine (finely ground and sieved)are stirred in and the reaction flask is subsequently rinsed withmethanol. The reaction mixture is then kept gently at the boil at a bathtemperature of 80° C. The temperature is raised to 100° C. whiledistilling off methanol. The reaction mixture is diluted with a further100 ml of o-dichlorobenzene and acidified with 20 ml of glacial aceticacid. The temperature is raised to 140°-145° C. and kept thereat for 2hours with good stirring. The pigment is collected by filtration at 120°C. and the filter cake is washed with methanol, acetone and water anddried, affording 18 g of a productive orange pigment which, in the formin which it is obtained or after it has been ground by one of theconventional methods, can be used for the preparation of lacquers andprinting pastes as well as for incorporation in plastics. The resultingorange colourations have outstanding fastness properties.

    ______________________________________                                        Analysis                                                                      ______________________________________                                        calculated    C 46.8    H 1.3     N 9.4                                       found         C 45.9    H 1.6     N 9.3                                       ______________________________________                                    

EXAMPLES 46 TO 56

Table II lists further pigments which are obtained by condensing anisoindolinone of the formula (IX), wherein Y₁ and Z₁ have the indicatedmeanings, with the tetraaminoazines also listed in the table.

                  TABLE II                                                        ______________________________________                                        No.  Y.sub.1                                                                              Z.sub.1  Tetraaminoazine  Shade                                   ______________________________________                                        46   Cl     Cl       4,4',3",3"'-tetraamino-tetra-                                                                  yellow                                                       phenylketazine                                           47   Cl     Cl       4,4',3",3"'-tetraamino-4",4"'-                                                                 orange                                                       dichlorotetraphenylketazine                              48   Cl     Cl       4,4'-diamino-4",4"'-di(o-amino-                                                                 "                                                           phenoxy)-tetraphenylketazine                             49   Cl     Cl       4,4'-diamino-4",4"'-di-(p-amino-                                                                "                                                           phenoxy)-tetraphenylketazine                             50   Cl     Cl       4,4'-diamino-4",4"'-di-(p-amino-                                                                "                                                           o-chlorophenoxy)-tetraphenyl-                                                 ketazine                                                 51   Cl     --OCH.sub.3                                                                            4,4',4",4"'-tetraamino-tetra-                                                                  yellowish                                                    phenylketazine   orange                                  52   Cl     Cl       4,4'-diamino-3",3"'-dichloro-                                                                  yellow                                                       4",4"'-di-[p-aminophenoxy-]-                                                  tetraphenylketazine                                      53   Cl     Cl       4,4'-diamino-3",3"'-dichloro-                                                                  yellow                                                       4",4"'-di-(o-chloro-p-amino-                                                  phenoxy)-tetraphenylketazine                             54   Cl     Cl       4,4'-diamino-3,3'-dimethyl-                                                                    yellow                                                       3",3"'-dichloro-4",4"'-di-                                                    (o-chloro-p-aminophenoxy)-                                                    tetraphenylketazine                                      55   Cl     Cl       4,4'-diamino-4",4"'-(p-amino-                                                                  orange                                                       phenyl)-tetraphenylketazine                              56   Cl     Cl       4,4'-diamino-3,3'-dimethyl-                                                                    orange                                                       3",3"'-dichloro-4",4"'-(p-                                                    aminophenoxy)-tetraphenyl-                                                    ketazine                                                 ______________________________________                                         Q = direct bond                                                          

EXAMPLE 57

The procedure of Example 1 is repeated using 11 g of the4,4"-diamino-4'-chloro-4"-methyltetraphenylketazine obtained inaccordance with Example 213 instead of 11,5 g of4,4"-diamino-4',4"'-dichloro-tetraphenylketazine. Yield: 23.2 g of amuch redder orange pigment which has similarly good properties whenincorporated into the different substrates.

EXAMPLES 58 TO 135

The following table lists further pigments which are obtained bycondensing 3,3-dimethoxy-4,5,6,7-tetrachloroisoindolinone-1 withdiamino-tetraphenylketazines of the formula ##STR20## wherein R₁ -R₆have the meanings indicated in the table.

                  TABLE                                                           ______________________________________                                        No     R.sub.1                                                                             R.sub.2                                                                              R.sub.3                                                                              R.sub.4                                                                            R.sub.5                                                                              R.sub.6                                                                            Shade                             ______________________________________                                        58    H      H      Cl     H    CH.sub.3                                                                             CH.sub.3                                                                           orange                            59    H      H      H      H    CH.sub.3                                                                             H    orange                            60    H      H      CH.sub.3                                                                             H    OCH.sub.3                                                                            H    scarlet                           61    H      H      H      H    Cl     H    orange                            62    H      H      Cl     H    Br     H    orange                            63    H      H      Br     H    H      H    orange                            64    H      H      CH.sub.3                                                                             H    Br     H    scarlet                           65    H      H      CH.sub.3                                                                             CH.sub.3                                                                           H      H    scarlet                           66    H      H      CH.sub.3                                                                             H    CH.sub.3                                                                             CH.sub.3                                                                           scarlet                           67    H      H      OCH.sub.3                                                                            H    H      H    scarlet                           68    H      H      Br     H    OCH.sub.3                                                                            H    orange                            69    H      H                                                                                     ##STR21##                                                                           H    CH.sub.3                                                                             H    orange                            70    H      H                                                                                     ##STR22##                                                                           H    H      H    orange                            71    H      H      CH.sub.3                                                                             CH.sub.3                                                                           OCH.sub.3                                                                            H    red                               72    H      H      Cl     H    OCH.sub.3                                                                            H    orange                            73    H      H      CH.sub.3                                                                             H    Cl     Cl   orange                            74    H      H      H      H    Cl     Cl   orange                            75    H      H      OCH.sub.3                                                                            H    Cl     Cl   orange                            76    CH.sub.3                                                                             H      Cl     H    H      H    orange                            77    H      H      Cl     Cl   CH.sub.3                                                                             CH.sub.3                                                                           orange                            78    H      H      Cl     Cl   Cl     H    orange                            79    CH.sub.3                                                                             H      Cl     H    OCH.sub.3                                                                            H    orange                            80    CH.sub.3                                                                             H      Cl     H    Cl     H    orange                            81    CH.sub.3                                                                             H      Cl     H    CH.sub.3                                                                             H    orange                            82    CH.sub.3                                                                             H      Cl     H    Br     H    orange                            83    H      H      Br     H    CH.sub.3                                                                             CH.sub.3                                                                           orange                            84    H      H      Br     H    Cl     Cl   orange                            85    CH.sub.3                                                                             H      H      H    H      H    scarlet                           86    CH.sub.3                                                                             H      CH.sub.3                                                                             H    H      H    scarlet                           87    CH.sub.3                                                                             H      CH.sub.3                                                                             H    Cl     H    orange                            88    CH.sub.3                                                                             H      H      H    OCH.sub.3                                                                            H    orange                            89    CH.sub.3                                                                             H      CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                             H    red                               90    CH.sub.3                                                                             H      CH.sub.3                                                                             CH.sub.3                                                                           OCH.sub.3                                                                            H    scarlet                           91    CH.sub.3                                                                             H      OCH.sub.3                                                                            H    CH.sub.3                                                                             H    scarlet                           92    CH.sub.3                                                                             H      CH.sub.3                                                                             H    CH.sub.3                                                                             H    scarlet                           93    CH.sub.3                                                                             H      CH.sub.3                                                                             H    OCH.sub.3                                                                            H    scarlet                           94    CH.sub.3                                                                             H      OCH.sub.3                                                                            H    OCH.sub.3                                                                            H    scarlet                           95    CH.sub.3                                                                             H      OCH.sub.3                                                                            H    H      H    scarlet                           96    CH.sub.3                                                                             H      H      H    CH.sub.3                                                                             H    scarlet                           97    CH.sub.3                                                                             H      OCH.sub.3                                                                            H    Cl     H    orange                            98    CH.sub.3                                                                             H      CH.sub.3                                                                             H    CH.sub.3                                                                             CH.sub.3                                                                           scarlet                           99    CH.sub.3                                                                             H      CH.sub.3                                                                             H    Br     H    orange                            100   CH.sub.3                                                                             H      OCH.sub.3                                                                            H    Br     H    orange                            101   CH.sub.3                                                                             H      H      H    CH.sub.3                                                                             CH.sub.3                                                                           scarlet                           102   CH.sub.3                                                                             H      CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                             CH.sub.3                                                                           red                               103   CH.sub.3                                                                             H      Cl     H    Cl     Cl   orange                            104   CH.sub.3                                                                             H      CH.sub.3                                                                             CH.sub.3                                                                           Br     H    orange                            105   CH.sub.3                                                                             H      Cl     H    CH.sub.3                                                                             CH.sub.3                                                                           orange                            106   CH.sub.3                                                                             H      OCH.sub.3                                                                            H    CH.sub.3                                                                             CH.sub.3                                                                           red                               107   CH.sub.3                                                                             H      H      H    Cl     Cl   orange                            108   CH.sub.3                                                                             H      H      H    Br     H    orange                            109   CH.sub.3                                                                             H      H      H    Cl     H    orange                            110   CH.sub.3                                                                             H      CH.sub.3                                                                             H    Cl     Cl   orange                            111   CH.sub.3                                                                             H      OCH.sub.3                                                                            H    Cl     Cl   orange                            112   CH.sub.3                                                                             H      CH.sub.3                                                                             CH.sub.3                                                                            ##STR23##                                                                           H    red                               113   CH.sub.3                                                                             H      OCH.sub.3                                                                            H                                                                                   ##STR24##                                                                           H    red                               114   CH.sub.3                                                                             CH.sub.3                                                                             Cl     H    H      H    orange                            115   CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                           H      H    red                               116   CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                             H    H      H    scarlet                           117   CH.sub.3                                                                             CH.sub.3                                                                             OCH.sub.3                                                                            H    H      H    red                               118   CH.sub.3                                                                             H      CH.sub.3                                                                             CH.sub.3                                                                           Cl     Cl   orange                            119   CH.sub.3                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                      H    CH.sub.3                                                                             H    red                               120   CH.sub.3                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                      H    OCH.sub.3                                                                            H    red                               121   CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                             H    Cl     H    orange                            122   CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                             H    OCH.sub.3                                                                            H    scarlet                           123   CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                             H    red                               124   CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                           OCH.sub.3                                                                            H    red                               125   CH.sub.3                                                                             CH.sub.3                                                                             OCH.sub.3                                                                            H    Cl     H    orange                            126   CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                           Cl     H    scarlet                           127   CH.sub.3                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                      H    H      H    scarlet                           128   CH.sub.3                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                      H    Cl     H    orange                            129   CH.sub.3                                                                             H      C.sub.2 H.sub.5                                                                      H    CH.sub.3                                                                             H    scarlet                           130   CH.sub.3                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                      H    CH.sub.3                                                                             CH.sub.3                                                                           red                               131   CH.sub.3                                                                             H      C.sub.2 H.sub.5                                                                      H    OCH.sub.3                                                                            H    red                               132   CH.sub.3                                                                             H      C.sub.2 H.sub.5                                                                      H    Cl     H    orange                            133   CH.sub.3                                                                             H      C.sub.2 H.sub.5                                                                      H    CH.sub.3                                                                             CH.sub.3                                                                           scarlet                           134   CH.sub.3                                                                             H      C.sub.2 H.sub.5                                                                      H                                                                                   ##STR25##                                                                           H    orange                            135   CH.sub.3                                                                             H      C.sub.2 H.sub.5                                                                      H    Br     H    orange                            ______________________________________                                    

EXAMPLE 136

A suspension of 92.4 g of 4-amino-4'-chlorobenzophenone, 1.5 g of zincchloride and 11 ml of hydrazine hydrate in 200 ml of ethylene glycolmonomethyl ether is heated for 22 hours to the boil, in the course ofwhich the internal temperature falls from 116° C. to 112° C. on accountof the water which forms, and the odour of hydrazine disappears. Then125 ml of a mixture of ethylene glycol monomethyl ether/water isdistilled off in the descending cooler in the course of 24 hours andsimultaneously 100 ml of solvent is added dropwise. The internaltemperature rises to 125° C. and a clear solution forms. On cooling, thereaction product crystallises out. The mass is diluted with 200 ml ofalcohol and filtered after brief standing. The filter cake is washedwith alcohol and dried, affording 65 g of4,4"-diamino-4',4"'-dichloro-tetraphenylketazine (71% of theory) with amelting point of 224°-227° C. A further 18.3 g of reaction product witha melting point of 221°-223° C. are obtained from the mother liquor byevaporating the solvent and stirring the residue in alcohol. The totalyield is accordingly 91%.

EXAMPLES 137 TO 212

Table III lists further ketazines of the formula ##STR26## which areobtained by condensing hydrazine hydrate with a benzophenone of theformula ##STR27## in ethylene glycol monomethyl ether. The position andnature of the substituents are indicated in columns 2 and 3 respectivelyof the table. In this connection it is to be observed that, depending ontheir constitution, the tetraphenylketazines are in the form ofdifferent stereoisomoic mixtures and can also be processed as such.

When using benzophenones which are difficult to condense, in particular2"- und 2"'-methyl-substituted benzophenones, it is advantageous toreplace ethylene glycol monomethyl ether by ethylene glycol monoethylether or diethylene glycol dimethyl ether, and to carry out the secondstep of the reaction at a temperature of 135° to 165° C.

                  TABLE III                                                       ______________________________________                                                                        Analysis                                           Position and nature                                                                             Melting  calc.                                         Ex.  of the substituents of                                                                          point    found                                         No.  A         B           in °C.                                                                        C%   H%   N%                                ______________________________________                                        137  2-amino    --         205-207                                                                              79.97                                                                              5.68 14.35                                                               79.8 5.8  14.3                              138  4-amino    --         223-226                                                                              79.97                                                                              5.68 14.35                                                               79.9 5.7  14.5                              139  3-amino   4-methyl    168-173                                                                              80.35                                                                              6.26 13.4                                                                79.6 6.3  13.4                              140  4-amino   "           240-245                                                                              80.35                                                                              6.26 13.4                                                                80.1 6.4  13.5                              141  4-amino-   --         238-240                                                                              80.35                                                                              6.26 13.4                                                                80.5 6.4  13.5                              142   "        4-methyl    256-259                                                                              80.68                                                                              6.77 12.54                                                               80.3 6.6  12.6                              143  4-amino   2,4-di-     200-203                                                                              80.7 6.77 12.54                                            methyl             80.2 6.9  12.5                              144   "        3.4-di-     198-200                                                                              80.7 6.77 12.54                                            methyl             80.4 6.9  12.5                              145  4-amino-  2,4-di-     202-204                                                                              80.97                                                                              7.2  11.8                                   3-methyl  methyl             80.9 7.3  12.0                              146   "        3.4-di-     230-232                                                                              80.97                                                                              7.2  11.8                                             methyl             80.4 7.3  11.8                              147  3-amino-   --         191-193                                                                              74.64                                                                              5.82 12.44                                  4-methoxy                    74.7 5.9  12.4                              148  4-amino   4-methoxy   233-236                                                                              74.64                                                                              5.82 12.44                                                               74.8 5.9  12.8                              149  4-amino-   "          220-223                                                                              75.3 6.3  11.7                                   3-methyl                     75.2 6.5  11.7                              150   "        4-methyl    175-177                                                                              75.3 6.3  11.7                                                                75.1 6.4  11.6                              151  3-amino-  4-methoxy   167-170                                                                              70.57                                                                              5.9  10.97                                  4-methoxy                    70.4 6.1  10.9                              152  4-amino   2,4-di-     240-241                                                                              70.57                                                                              5.9  10.97                                            methoxy            70.5 5.9  10.8                              153   "        3,4-di-     218-221                                                                              70.57                                                                              5.9  10.97                                            methoxy            70.4 6.0  11.0                              154  4-amino   4-ethoxy    219-221                                                                              75.3 6.3  11.7                                                                75.3 6.7  11.5                              155   "        4-isopro-   197-199                                                                              80.97                                                                              7.2  11.8                                             poxy               80.3 7.3  12.3                              156   "        4-tert-     157-160                                                                              81.2 7.6  11.15                                            butyl              81.0 7.7  11.1                              157  4-amino-   --         211-212                                                                              68.0 4.4  12.2                                   2-chloro                     68.0 4.6  12.0                              158  4-amino   4-bromo     232-245                                                                              56.95                                                                              3.6  10.2                                                                57.1 3.7  10.4                              159  2-amino-   "          227-230                                                                              58.35                                                                              4.2  9.7                                    3-methyl                     58.5 4.2  9.9                               160   "        4-chloro    216-219                                                                              69.0 4.96 11.5                                                                68.7 5.1  11.6                              161  4-amino-  4-methyl    266-268                                                                              69.0 4.96 11.5                                   2-chloro                     68.9 5.1  11.8                              162   "        4-methoxy   223-226                                                                              64.75                                                                              4.66 10.8                                                                64.9 4.6  10.9                              163  3-amino-  4-chloro    200-203                                                                              64.76                                                                              4.66 10.8                                   4-methoxy                    64.6 4.8  11.0                              164  3-amino-  4-ethoxy    170-173                                                                              65.8 5.15 10.2                                   4-chloro                     65.7 5.2  10.5                              165  4-amino-  4-bromo     234-235                                                                              50.6 2.94 9.08                                   2-chloro                     51.0 2.9  9.2                               166  3-amino-  4-chloro    213-215                                                                              59.1 3.4  10.6                                   4-chloro                     59.3 3.3  10.7                              167  2-chloro                     59.3 3.6  10.8                              168  4-amino   2,4-di-     242-245                                                                              59.1 3.4  10.6                                             chloro             58.9 3.7  10.4                              169  4-amino   3,4-di-     194-198                                                                              59.1 3.4  10.6                                             chloro             58.5 3.6  10.6                              170  4-amino-  2,4-di-     222-224                                                                              60.45                                                                              4.0  10.07                                  3-methyl  chloro             60.4 4.1  10.0                              171  4-amino-  3,4-di-     219-221                                                                              60.45                                                                              4.0  10.07                                  3-methyl  chloro             60.4 4.2  10.1                              172  4-amino   4-phenyl    261-263                                                                              84.1 5.57 10.3                                                                83.7 5.6  10.4                              173   "        4-phenoxy   206-208                                                                              79.4 5.26 9.75                                                                79.2 5.1  9.8                               174  4-amino-  4-phenyl    285-288                                                                              84.18                                                                              6.0  9.8                                    3-methyl                     83.5 6.1  9.8                               175   "        4-phenoxy   208-210                                                                              79.7 5.7  9.3                                                                 79.3 5.8  9.4                               176  3-amino   3-amino     223-224                                                                              74.26                                                                              5.75 20.0                                                                74.2 5.7  19.9                              177  4-amino   3-amino     247-250                                                                              74.26                                                                              5.76 20.0                                                                74.1 6.0  20.2                              178   "        4-amino     295-298                                                                              74.26                                                                              5.75 20.0                                                                73.6 5.8  19.9                              179  3-amino-  3-amino-    202-205                                                                              66.65                                                                              5.97 15.55                                  4-methoxy 4-methoxy          66.5 6.0  15.7                              180  4-amino   3-amino-    243-246                                                                              63.93                                                                              4.63 17.2                                             4-chloro           63.6 4.7  17.2                              181   "        4-o-amino-  215-217                                                                              75.48                                                                              5.33 13.9                                             phenoxy            74.8 5.5  13.6                              182   "        4-p-amino-  285-287                                                                              75.48                                                                              5.33 13.9                                             phenoxy            75.2 5.7  13.6                              183  4-amino-   "          200-203                                                                              75.9 5.7  13.28                                  3-methyl                     75.4 5.6  13.1                              184  4-amino   4-o-amino-  204-207                                                                              67.76                                                                              4.5  12.48                                            p-chloro-          67.3 4.5  12.2                                             phenoxy                                                        185   "        4-o-chloro- 245-248                                                                              67.76                                                                              4.5  12.48                                            p-amino-           67.8 4.6  12.4                                             phenoxy                                                        186  4-amino-  4-o-chloro- 242-245                                                                              68.47                                                                              4.88 11.98                                  3-methyl  p-amino-           68.3 4.9  11.8                                             phenoxy                                                        187   "        4-o-amino-  213-216                                                                              68.47                                                                              4.88 11.98                                            p-chloro-          68.2 4.9  11.70                                            phenoxy                                                        188  4-amino   3-chloro-4- 288-291                                                                              67.76                                                                              4.5  12.48                                            p-amino-           67.6 4.5  12.4                                             phenoxy                                                        189   "        3-chloro-4- 206-209                                                                              61.47                                                                              3.8  11.3                                             o-chloro-p-        61.5 4.0  10.8                                             amino-                                                                        phenoxy                                                        190  4-amino   4-fluoro    193-197                                                                              73.23                                                                              4.7  13.14                                                               72.8 4.6  13.5                              191  4-amino   4-ethyl     217-219                                                                              80.68                                                                              6.77 12.54                                                               80.1 6.8  12.5                              192  4-amino-  3-chloro-4- 158-160                                                                              62.35                                                                              4.2  10.9                                   3-methyl  (o-chloro-p-       62.0 4.3  11.0                                             aminophenoxy)                                                  193  4-amino   4-(p-amino- >300   79.7 5.6  14.67                                            phenyl)            79.4 5.7  14.5                              194  4-amino   2,5-di-     253-256                                                                              70.57                                                                              5.9  10.97                                            methoxy            70.1 6.0  10.9                              195  4-amino-  4-fluoro    255-257                                                                              74.0 5.3  8.36                                   3-methyl                     73.7 5.4  8.2                               196  4-amino   2,5-di-     256-260                                                                              69.9 5.47 10.87                                            methyl-            69.4 5.6  10.7                                             4-chloro                                                       197  4-amino-  4-cyclo-    177-180                                                                              82.43                                                                              7.96 9.6                                    3-methyl  hexyl              82.0 8.1  9.6                               198  4-amino   4-cyclo-    214-218                                                                              82.27                                                                              7.6  10.1                                             hexyl              81.9 7.5  9.9                               199  4-amino   2,5-di-     238-242                                                                              62.18                                                                              4.87 9.67                                             methoxy-           61.9 4.9  9.8                                              4-chloro                                                       200  4-amino   2,5-di-     241-245                                                                              80.68                                                                              6.77 12.54                                            methyl             80.6 6.9  12.5                              201  4-amino-  4-ethoxy    223-226                                                                              75.86                                                                              6.76 11.06                                  3-methyl                     75.8 6.9  11.3                              202  4-amino-  4-ethyl     221-225                                                                              80.97                                                                              7.22 11.8                                   3-methyl                     80.7 7.3  12.0                              203  4-amino-  4-(p-chloro-                                                                              195-198                                                                              71.5 4.8  8.3                                    3-methyl  phenoxy)           71.6 5.0  8.3                               204  4-amino-  2,5-di-     192-198                                                                              70.7 5.9  10.3                                   3-methyl  methyl-                                                                       4-chloro                                                       205  4-amino-  2,5-di-     210-211                                                                              71.35                                                                              6.36 10.4                                   3-methyl  methoxy            71.2 6.4  10.5                              206  4-amino-  2,4-di-     219-220                                                                              71.35                                                                              6.36 10.4                                   3-methyl  methoxy            71.4 6.5  10.5                              208  4-amino-  2,5-di-     216-219                                                                              63.26                                                                              5.31 9.22                                   3-methyl  methoxy-           62.8 5.5  9.0                                              4-chloro                                                        ##STR28##                                                                    209  4-amino    --         192-196                                                                              84.1 5.57 10.32                                                               84.7 5.4  10.2                              210  4-amino   4-methyl    230-233                                                                              84.18                                                                              6.01 9.92                                                                84.0 5.9  9.6                               211  4-amino   4-methoxy   228-231                                                                              79.71                                                                              5.69 9.3                                                                 79.3 5.8  9.1                               212  4-amino   4-chloro    215-220                                                                              74.6 4.6  9.16                                                                74.1 4.7  9.2                               ______________________________________                                    

EXAMPLE 213

To a suspension of 23.1 g of 4-amino-4'-chlorobenzophenone in 100 ml ofethylene glycol monomethyl ether are added 0.75 g of zinc chloride and5.5 ml of hydrazine hydrate. The reaction mixture is boiled overnight ata bath temperature of 150° C., in the course of which the boilingtemperature falls from 118° C. to 115° C. on account of the water whichforms. Then 21.1 g of 4-amino-4'-methylbenzophenone are added to theresulting turbid solution. Then 21 ml of solvent are distilled off at abath temperature of 160° C. and the internal temperature rises to122°-125° C. This temperature is kept for 24 hours, whereupon a portionof the reaction product crystallises out. After cooling, the resulting4,4"-diamino-4'-chloro-4"'-methyltetraphenylketazine is collected byfiltration, washed with alcohol and water and dried in vacuo at 80° C.,affording 30 g (68%) of reaction product with a melting point of225°-226° C.

    ______________________________________                                        Analysis                                                                      ______________________________________                                        calculated                                                                             C 73.88% H 5.28%   N 12.76% Cl 8.08%                                 found    73.7%    5.3%      13.00%   7.8%                                     ______________________________________                                    

Table IV lists further ketazines of the formula ##STR29## which areobtained by condensing 1 mole of 4-amino-benzophenone of the formula##STR30## and 1 mole of 4-aminobenzophenone of the formula ##STR31##with 1 mole of hydrazine hydrate in ethylene glycol.

                                      TABLE IV                                    __________________________________________________________________________    Ex.                        Analysis                                           No. A   B   C    D    m.p.(°C.)                                                                   C   H   N                                          __________________________________________________________________________    214 --  --  --   4-CH.sub.3                                                                         196-199°                                                                    80.17                                                                             5.98                                                                              13.85                                                                 79.8                                                                              6.1 13.7                                       215 --  --  4-CH.sub.3                                                                         4-OCH.sub.3                                                                        217-221°                                                                    77.39                                                                             6.03                                                                              12.89                                                                 77.3                                                                              6.2 12.8                                       216 --  --  --   4-Cl 190-192°                                                                    73.49                                                                             4.98                                                                              13.19                                                                 73.0                                                                              5.0 13.0                                       217 --  --  4-Cl 4-Br 222-224°                                                                    61.98                                                                             4.0 11.12                                                                 61.8                                                                              4.2 11.2                                       218 --  --  --   4-Br 177-182°                                                                    66.35                                                                             4.51                                                                              11.94                                                                 66.1                                                                              4.6 11.9                                       219 --  --  4-CH.sub. 3                                                                        4-Br 233-235°                                                                    67.09                                                                             4.8 11.59                                                                 67.5                                                                              5.0 11.7                                       220 --  --  4-CH.sub. 3                                                                        3,4-di-                                                                            204-208°                                                                    80.5                                                                              6.5 12.95                                                       CH.sub.3  80.3                                                                              6.6 12.9                                       221 --  --  4-Br 4-OCH.sub.3                                                                        212-218°                                                                    64.94                                                                             4.64                                                                              11.22                                                                 64.8                                                                              4.7 11.2                                       222 --  --                                                                                 ##STR32##                                                                         --   178-183°                                                                    82.37 81.9                                                                        5.62 5.7                                                                          12.01 11.7                                 223 --  --  4-OCH.sub.3                                                                        3,4-di-                                                                            198-201°                                                                    77.65                                                                             6.29                                                                              12.49                                                       CH.sub.3  77.3                                                                              6.2 12.5                                       224 --  --  4-Cl 4-OCH.sub.3                                                                        208-212°                                                                    71.28                                                                             5.09                                                                              12.31                                                                 71.0                                                                              5.2 12.2                                       225 3-CH.sub.3                                                                        --  4-Cl --   168-173°                                                                    73.88                                                                             5.28                                                                              12.76                                                                 73.5                                                                              5.3 12.7                                       226 --  --  3,4-di-                                                                            3,4-di-                                                                            194-197°                                                                    69.0                                                                              4.96                                                                              11.5                                                   CH.sub.3                                                                           Cl        68.7                                                                              5.1 11.5                                       227 --  --  4-Cl 3,4-di-                                                                            188-192°                                                                    63.24                                                                             3.88                                                                              11.35                                                       Cl        63.2                                                                              4.1 11.5                                       228 3-CH.sub.3                                                                        --  4-Cl 4-Cl 148-155°                                                                    68.5                                                                              4.7 11.84                                                                 68.3                                                                              4.9 11.8                                       229 3-CH.sub.3                                                                        --  4-Cl 4-CH.sub.3                                                                         179-187°                                                                    74.24                                                                             5.56                                                                              12.37                                                                 73.6                                                                              5.6 12.3                                       230 3-CH.sub.3                                                                        --  4-Cl 4-Br 176-181°                                                                    62.62                                                                             4.28                                                                              10.82                                                                 62.4                                                                              4.4 10.9                                       231 --  --  4-Br 3,4-di-                                                                            187-191°                                                                    67.61                                                                             5.07                                                                              11.26                                                       CH.sub.3  67.1                                                                              5.2 11.0                                       232 --  --  4-Br 3,4-di-                                                                            190-198°                                                                    58.02                                                                             3.56                                                                              10.4                                                        Cl        57.8                                                                              3.7 10.3                                       233 3-CH.sub.3                                                                        --  --   --   202-208°                                                                    80.17                                                                             6.0 13.85                                                                 80.1                                                                              6.2 13.8                                       234 3-CH.sub.3                                                                        --  3,4-di-                                                                            4-CH.sub.3                                                                         --   80.68                                                                             6.77                                                                              12.54                                                  CH.sub.3       80.6                                                                              6.8 12.4                                       235 3-CH.sub.3                                                                        --  3,4-di-                                                                            4-OCH.sub.3                                                                        196-205°                                                                    77.89                                                                             6.54                                                                              12.11                                                  CH.sub.3       77.3                                                                              6.6 12.2                                       236 3-CH.sub.3                                                                        --  4-OCH.sub.3                                                                        4-CH.sub.3                                                                         190-195°                                                                    77.65                                                                             6.3 12.5                                                                  77.3                                                                              6.3 12.5                                       237 3-CH.sub.3                                                                        --  4-CH.sub.3                                                                         4-CH.sub.3                                                                         229-234°                                                                    80.52                                                                             6.53                                                                              12.95                                                                 80.5                                                                              6.6 12.6                                       238 3-CH.sub.3                                                                        --  4-CH.sub.3                                                                         4-OCH.sub.3                                                                        --   77.65                                                                             6.3 12.5                                                                  77.2                                                                              6.4 12.4                                       239 3-CH.sub.3                                                                        --  4-OCH.sub.3                                                                        4-OCH.sub.3                                                                        192-199°                                                                    74.97                                                                             6.07                                                                              12.06                                                                 74.4                                                                              6.1 11.9                                       240 3-CH.sub.3                                                                        --  --   4-CH.sub.3                                                                         --   80.35                                                                             6.26                                                                              13.39                                                                 79.9                                                                              6.2 13.3                                       241 3-CH.sub.3                                                                        --  4-OCH.sub.3                                                                        4-Cl 183-187°                                                                    71.71                                                                             5.37                                                                              11.95                                                                 71.2                                                                              5.5 12.0                                       242 3-CH.sub.3                                                                        --  4-CH.sub.3                                                                         3,4-di-                                                                            228-237°                                                                    80.68                                                                             6.77                                                                              12.54                                                       CH.sub.3  80.4                                                                              6.8 12.5                                       243 3-CH.sub.3                                                                        --  4-CH.sub.3                                                                         4-Br --   67.61                                                                             5.07                                                                              11.26                                                                 67.3                                                                              5.2 11.3                                       244 3-CH.sub.3                                                                        --  --   3,4-di-                                                                            --   80.5                                                                              6.5 12.95                                                       CH.sub.3  79.9                                                                              6.2 13.0                                       245 3-CH.sub.3                                                                        --  3,4-di-                                                                            3,4-di-                                                                            205-215°                                                                    80.83                                                                             7.0 12.16                                                  CH.sub.3                                                                           CH.sub.3  80.6                                                                              7.0 12.1                                       246 3-CH.sub.3                                                                        --  4-Cl 3,4-di-                                                                            166-170°                                                                    63.86                                                                             4.17                                                                              11.03                                                       Cl        64.0                                                                              4.2 11.2                                       247 3-CH.sub.3                                                                        --  3,4-di-                                                                            4-Br 190-205°                                                                    68.1                                                                              5.3 10.95                                                  CH.sub.3       68.5                                                                              5.5 11.0                                       248 3-CH.sub.3                                                                        --  4-Cl 3,4-di-                                                                            --   74.58                                                                             5.83                                                                              12.0                                                        CH.sub.3  73.8                                                                              5.7 11.9                                       249 3-CH.sub.3                                                                        --  4-OCH.sub.3                                                                        3,4-di-                                                                            190-196°                                                                    77.89                                                                             6.53                                                                              12.1                                                        CH.sub.3  77.4                                                                              6.6 12.0                                       250 3-CH.sub.3                                                                        --  --   3,4-di-                                                                            --   68.5                                                                              4.7 11.84                                                       Cl        68.6                                                                              4.7 12.1                                       251 3-CH.sub.3                                                                        --  4-CH.sub.3                                                                          ##STR33##                                                                         --   82.56 82.1                                                                        6.11 6.1                                                                          11.33 11.1                                 252 3-CH.sub.3                                                                        --  3,4-di- CH.sub.3                                                                    ##STR34##                                                                         --   82.64 82.1                                                                        6.34 6.3                                                                          11.01 10.9                                 253 3-CH.sub.3                                                                        3-CH.sub.3                                                                        4-Cl --   186-193°                                                                    74.24                                                                             5.56                                                                              12.37                                                                 74.0                                                                              5.7 12.4                                       254 3-CH.sub.3                                                                        3-CH.sub.3                                                                        3,4-di-                                                                            --   --   80.68                                                                             6.77                                                                              12.54                                                  CH.sub.3       80.4                                                                              6.7 12.4                                       255 3-CH.sub.3                                                                        3-CH.sub.3                                                                        4-C.sub.2 H.sub.5                                                                  4-CH.sub.3                                                                         227-231°                                                                    80.83                                                                             7.0 12.16                                                                 80.9                                                                              7.1 12.4                                       256 3-CH.sub.3                                                                        3-CH.sub.3                                                                        4-C.sub.2 H.sub.5                                                                  4-OCH.sub.3                                                                        228-230°                                                                    78.12                                                                             6.77                                                                              11.75                                                                 77.9                                                                              6.8 11.7                                       257 3-CH.sub.3                                                                        3-CH.sub.3                                                                        4-CH.sub.3                                                                         4-Cl 236-240°                                                                    74.58                                                                             5.83                                                                              12.0                                                                  75.0                                                                              6.1 12.1                                       258 3-CH.sub.3                                                                        --  4-CH.sub.3                                                                         --   --   80.35                                                                             6.26                                                                              13.39                                                                 80.2                                                                              6.4 13.3                                       259 3-CH.sub.3                                                                        3-CH.sub.3                                                                        4-CH.sub.3                                                                         4-OCH.sub.3                                                                        234-238°                                                                    77.89                                                                             6.54                                                                              12.11                                                                 77.8                                                                              6.7 12.2                                       260 3-CH.sub.3                                                                        3-CH.sub.3                                                                        3,4-di-                                                                            4-CH.sub.3                                                                         232-234°                                                                    80.83                                                                             7.0 12.16                                                  CH.sub.3       81.0                                                                              7.2 12.3                                       261 3-CH.sub.3                                                                        3-CH.sub.3                                                                        3,4-di-                                                                            4-OCH.sub.3                                                                        214-217°                                                                    78.12                                                                             6.77                                                                              11.75                                                  CH.sub.3       78.2                                                                              6.8 11.7                                       262 3-CH.sub.3                                                                        3-CH.sub.3                                                                        4-OCH.sub.3                                                                        4-Cl 207-210°                                                                    72.11                                                                             5.63                                                                              11.6                                                                  71.9                                                                              5.7 11.6                                       263 3-CH.sub.3                                                                        3-CH.sub.3                                                                        3,4-di-                                                                            4-Cl 198-204°                                                                    74.91                                                                             6.08                                                                              11.65                                                  CH.sub.3       75.2                                                                              6.3 11.6                                       264 3-CH.sub.3                                                                        3-CH.sub.3                                                                        4-C.sub.2 H.sub.5                                                                  --   --   80.68                                                                             6.77                                                                              12.54                                                                 80.6                                                                              6.9 12.5                                       265 3-CH.sub.3                                                                        3-CH.sub.3                                                                        4,C.sub.2 H.sub.5                                                                  4-Cl 205-210°                                                                    74.91                                                                             6.08                                                                              11.65                                                                 75.4                                                                              6.3 11.5                                       266 3-CH.sub.3                                                                        --  4-C.sub.2 H.sub.5                                                                  4-CH.sub.3                                                                         --   80.68                                                                             6.77                                                                              12.54                                                                 80.1                                                                              6.8 12.7                                       267 3-CH.sub.3                                                                        3-CH.sub.3                                                                        4-C.sub.2 H.sub.5                                                                  3,4-di-                                                                            203-207°                                                                    80.97                                                                             7.22                                                                              11.8                                                        CH.sub.3  80.4                                                                              7.3 11.5                                       268 3-CH.sub.3                                                                        --  4-C.sub.2 H.sub.5                                                                  4-OCH.sub.3                                                                        197-204°                                                                    77.89                                                                             6.54                                                                              12.11                                                                 77.6                                                                              6.6 12.0                                       269 3-CH.sub.3                                                                        --  4-C.sub.2 H.sub.5                                                                  --   --   80.52                                                                             6.5 12.95                                                                 80.0                                                                              6.5 12.7                                       270 3-CH.sub.3                                                                        --  4-C.sub.2 H.sub.5                                                                  4-Cl --   74.58                                                                             5.83                                                                              12.0                                                                  74.5                                                                              6.1 11.9                                       271 3-CH.sub.3                                                                        --  4-C.sub.2 H.sub.5                                                                  3,4-di-                                                                            --   80.83                                                                             7.0 12.16                                                       CH.sub.3  80.3                                                                              7.1 11.8                                       272 3-CH.sub.3                                                                        --  4-C.sub.2 H.sub.5                                                                  4-Br --   68.1                                                                              5.3 10.95                                                                 68.4                                                                              5.5 10.8                                       __________________________________________________________________________

EXAMPLE 273

2 g of the pigment obtained in Example 45 are ground with 36 g of tonerdehydrate, 60 g of boiled linseed oil of medium viscosity and 2 g ofcobalt linoleate on a three roll mill. The orange prints obtained withthe resulting colour paste are strong and outstandingly fast to light.

EXAMPLE 274

0.6 g of the pigment obtained in Example 1 is mixed with 67 g ofpolyvinyl chloride, 33 g of dioctyl phthalate, 2 g of dibutyl tindilaurate and 2 g of titanium dioxide and the mixture is processed to athin sheet for 15 minutes at 160° C. on a roll mill. The orangecolouration obtained is strong and fast to migration, heat and light.

EXAMPLE 275

10 g of titanium dioxide and 2 g of the pigment obtained in Example 5are ground for 48 hours in a ball mill with 88 g of a mixture of 26.4 gof coconut alkyl resin, 24 g of melamine/formaldehyde resin (30% solidscontent), 8.8 g of ethylene glycol monomethyl ether and 28.8 g ofxylene. The resulting lacquer is sprayed onto an aluminium sheet,predried for 30 minutes at room temperature and then stoved for 30minutes at 120° C., to give a yellow finish which has very good colourstrength and is distinguished by very good fastness to overstripebleeding, light and atmospheric influences.

EXAMPLE 276

8.03 g of 3-iminoisoindolin-1-one are added to a hot solution of 12.3 gof 4,4"-diamino-3',4',3"',4"'-tetrachloro-tetraphenylketazine in 150 mlof glacial acetic acid. The reaction mixture is boiled for 10 minutes,whilst the pigment begins to precipitate after about 30 seconds. Theprecipitate is collected by filtration, washed with methanol, acetoneand water and then dried, affording 15.7 g of a yellow pigment which,after it has been ground by one of the conventional methods, can be usedfor colouring plastics and for the preparation of lacquers and printingpastes. The resulting colourations are strong and distinguished byoutstanding fastness properties.

    ______________________________________                                        Analysis                                                                      ______________________________________                                        calculated                                                                            C 64.14%  H 3.08%   N 10.69% Cl 18.03%                                found   C 64.4%   H 3.22%   N 10.5%  Cl 17.65%                                ______________________________________                                    

EXAMPLE 277

6.7 g of 4,5-dichloro-2-cyanobenzoic acid methyl ester with a meltingpoint of 129°-130° C. (prepared by the process of Example 1 of BritishPat. No. 1,319,731 by reaction of the ammonium salt of4,5-dichloro-2-cyanobenzoic acid with dimethyl sulfate) are stirred for2 hours at room temperature with 28.75 ml of 1 N sodium methylatesolution in methanol, whereupon a suspension of the sodium salt of3,3-dimethoxy-5,6-dichloroisoindolin-1-one forms. Then 6.8 g of finelyground 4,4"-diamino-4',4"'-dibromo-tetraphenylketazine and 150 ml ofo-dichlorobenzene are added and the methyl alcohol is distilled off at abath temperature of 110° C., while the internal temperature rises in thecourse of 2 hours to 100° C. The sodium salt of the pigment begins toprecipitate at 80° C., without the ketazine having dissolved completely.The batch is diluted with a further 50 ml of o-dichlorobenzene and thetemperature is kept at 100° C. for 3 hours. After acidification with 10ml of glacial acetic acid, the internal temperature is raised to140°-150° C. and the mixture is stirred for 2 hours at this temperature.The insoluble pigment is collected by filtration at 120° C. The filtercake is washed with methanol, acetone and water and dried.

Yield: 9.5 g of a productive yellow pigment which, after incorporationinto plastics, printing pastes and lacquers, produces colourationsdistinguished by outstanding fasteness properties.

    ______________________________________                                        Analysis                                                                      ______________________________________                                        calculated                                                                            C 53.4%  H 2.5%   N 8.9% Cl 15.0%                                                                             Br 16.9%                              found   C 53.3%  H 2.6%   N 8.8% Cl 14.7%                                                                             Br 16.7%                              ______________________________________                                    

What is claimed is:
 1. An amine of the formula ##STR35## wherein R andR" represent hydrogen, halogen, methyl or methoxy, R₁, R₂, R₄ and R₅represent hydrogen, chlorine, bromine or alkyl of 1 to 2 carbon atoms,R₃ ' and R₆ ' represent hydrogen, halogen, alkyl or alkoxy groups of 1to 2 carbon atoms, or amino, Q is a direct bond or p-phenylene, n is 1or 2 and X represents a group of the formula ##STR36## wherein R₇ and R₈represent hydrogen, chlorine or methyl and the O of the phenoxy group isattached to the phenyl ring of said amine.
 2. Amines according to claim1, wherein the NH₂ groups are in the para-position to the ##STR37##group.